Certain tfflozolylurea compounds

ABSTRACT

A THIAZOLE DERIVATIVES HAVING THE GENERAL FORMULA   2-(R2-N(-R3)-C(=Z)-N(-R1)-),4-X,5-Y-THIAZOLE   AND PESTICIDAL COMPOSITIONS CONTAINING THE SAME.

United States Patent 01 lice Re. 27,506 Reissued Oct. 10, 1972 27,506CERTAIN TI-IIOZOLYLUREA COMPOUNDS Jean Claude Guillot, Eaubonne, PierrePoignant, Lyon, and Jacques de Bazelaire de Lesseux, Rueil-Malmaison,France, by Produits Chimiques Pechiney-Saiut-Gobain, Neuilly-sur-Seine,France, assignee No Drawing. Original No. 3,551,442, dated Dec. 29,1970, Ser. No. 540,192, Apr. 5, 1966. Application for reissue May 18,1971, Ser. No. 144,696

Int. Cl. C07d 91/34 US. Cl. ll-306.8 R Claims Matter enclosed in heavybrackets II] appears in the original patent but forms no part of thisreissue specification; matter printed in italics indicates the additionsmade by reissue.

ABSTRACT OF THE DISCLOSURE A thiazole derivative having the generalformula and pesticidal compositions containing the same.

This invention relates to a new family of compounds which arederivatives of thiazole and it relates also to the use of the thiazolederivatives as pesticides and especially as herbicides,

It is an object of this invention to produce and to provide a method forproducing thiazole derivatives of the type described and the use of suchthiazole derivatives as a pesticide and/ or a herbicide.

The thiazole derivatives embodying features of this invention may becharacterized by the formula in which X and Y are groups which may beidentical one with the other or different from each other, X and Y arerepersentative of such groups as hydrogen, halogen such as chlorine,bromine, iodine, thiocyanate, CN, COOH, an alkoxycarbonyl group, NHg,OH, a hydroxyalkyl, alkyl or alkoxy group containing from 1 to 4 carbonatoms such as methyl, ethyl, propyl, butyl, ethoxy, methoxy and the likein which the hydroxyalkyl, alkyl or alkoxy group can be unsubstituted orsubstituted with a halogen, an aryl group such as phenyl, naphthyl, ahalogenated aryl group, an alkaryl group such as benzyl, tolyl and thelike, an alkoxy aryl group, a halogenated alkaryl group, a halogenatedalkoxyaryl group, an aryloxy group, a halogenated aryloxy group and analkaryloxy group; in which Z is an atom selected from the groupconsisting or oxygen and sulphur; in which R is a group such as hydrogenor an alkyl, alkynyl, alkoxy, alkenyl or alkenoxy group having from 1 to4 carbon atoms, an alkylated acyl residue, a halogenated alkylated acylresidue, an aracyl, a halogenated aracyl (arylated acyl), an alkarylatedacyl, or an alkoxy-aryl group; in which R: and R is a group selectedfrom hydrogen, an alkyl group, an alkoxy group, an alkenyl group, analkenoxy group or an alkynyl group in which the groups contain from 1 to4 carbon atoms, an alkaryl residue, a halogenated alkaryl residue, anaryl group, a halogenated aryl group or an aryloxy group but in which R;and R are not both hydrogen in the same compound.

The compounds defined above, which fall within the scope of theinvention, may be prepared by a number of synthetic methods dependingsomewhat upon the nature of the groups R,, R and R The following willset forth typical examples of methods for the preparation of suchcompounds:

(1) When two of the three radicals R R and R are hydrogen, for examplewhen R and R are hydrogen while R is alky group, aryl group, or alkarylgroup, a halogenated alkaryl group or a halogenated aryl group, twomethods of preparation can be employed:

(a) The reaction of an alkyl or aryl isocyanate or isothiocyanate with aZ-aminothiazole in which X and Y are substituted groups, as illustratedin the following equation:

(b) The reaction of a mouosubstituted carbamyl or thiacarbamyl halide,in which the halogen is preferably chlorine, with a Z-aminothiazole inthe presence of an agent which binds the acid liberated during thereaction. in accordance with the equation:

(2) When ony one of the three radicals R R and R is hydrogen, such aswhen R is hydrogen and R, and R, represent one of the groups of alkyl,aryl, alkaryl, halogenated alkaryl or halogenated aryl groups, thefollowing process may be,emp1oyed for the preparation.

A carbamyl or thiacarbamyl halide, preferably the chloride, in which R,and R have the meaning given above, is reacted with a suitablysubstituted Z-aminothiazole in the presence of an agent that takes upthe acid liberated according to the equation:

X N l (3) When R is one of the groups selected from an alkylated acyl,halogenated alkylated acyl, arylacyl, halogenated arylacyl, alkylatedarylacyl and alkoxylated arylacyl and when R and R are selected from oneor more of the groups of hydrogen, alkyl, aryl, alkaryl, halogenatedaryl or halogenated alkaryl except that R and R cannot both be hydrogenin the same compound, the following may be employed:

The halide of an aliphatic or aromatic acid, preferably the chloride,R,Cl, is reacted with thiazolyl or the thiazolyl-thiourea derivativeprepared in accordance with method (1) or (2), as illustrated by thefollowing equation:

In the reaction outlined above, in which an acid is formed with anactive hydrogen atom, it is preferred to carry out the reactions in thepresence of an acid acceptor like a tertiary amine such astriethylamine, dimethylaniline or pyridine.

The derivatives of thiazolylurea or thiazolylthiourea are generallysolids which are readily soluble in organic solvents such as dimethylsulfoxide (DMSO), dimethylformamide, pyridine, tetrahydrofuran and CI-l-CN.

The following compounds are given by way of illustration, but not by wayof limitation, of the formulations representing compounds of thisinvention:

N- (Z-thiazolyl -N'-methylurea;

N-(Z-thiazolyl -N', -dimethylurea;

N-(Z-thiazolyl -N'-methyl-N'-methoxyurea;

N- Z-thiazolyl -N'-phenylurea;

N- Z-thiazolyl -N-methyl-N'-propenylu rea;

N-(Z-thiazolyl -N'-benzoyl-N',N'-dimethylurea;

N- Z-thiazolyl -N-rnethyl-N'-phenoxyurea;

N- Z-thiazolyl -N-butenyl-N'-ethylurea;

N- 2-thiazolyl -N-trichloroacetyl-N-butylu rea;

N-2 -chlorothiazolyl -N,N-dimethylu rea;

N-2 5-chlorothiazolyl -N'-methylurea;

N-Z 5 -chlorothiazolyl -N-methylthiourea;

N-Z 5-chloro-4-methylthiazolyl )-N'-phenylurea;

N-2 S-chloro-4-methylthiazolyl) -N'-methylurea;

N-2 5-chloro-4-methylthiazolyl) -N',N'-dimethylur ea;

N-2 (4, S-dichlo rothiazolyl) -N'-rnethylurea;

N- 2 (4,5-dichlorothiazolyl) -N,N'-dimethylurea;

N-2 4-trifiuoromethylthiazo lyl -N-methyl-N- methoxyurea;

N-Z (4-trifluor omethylthiazolyl -N'-methylurea;

N-2 4 (Z-chloro-ethyl) thiazolyl] N-ethylurea;

N-2 S-bromothiazolyl -N'-butynylurea;

N-2 4-chlorothiazolyl) -N'-methylurea;

N-2(4-ch1orothiazolyl -N',N'-dimethylurea;

N-2 (4chlorothiazolyl -N-monochloroaoetyhN-methyl- N-phenylurea;

N-2 (4-chlorornethylthiazolyl) -N',N'-dimethylurea;

N-Z 4-chloromethylthiazolyl) -N '-methylurea;

N-2 S-thiocyanatothiazolyl -N'-methy1urea;

N-2 (4-phenyl-5-thiocyanatothiazolyl) -N'-propenylurea;

N-2 (5-carbethoxy-4-me thylthiazo lyl )-N'-methylurea;

N-2 (4-2-hydroxyethylthiazolyl -N'- (2,4-dichlorophenoxy) urea;

N-Z 4-methylthiazolyl -N'-methylurea;

N-2 4-methylthiazolyl) -N',N'-dimethylurea;

N-2 (4-methylthiazolyl -N-phenylurea;

N-Z S-methylthiazolyl -N'-methylurea;

N-2 S-methylthiazolyl) -N',N'-dimethylurea;

N-2 (4-methylthiaaolyl -N'-methyl-N'-methoxyurea;

N-Z 4,5-dimethylthiazolyl -N'-methylurea;

N-2 4,5 -dimethylthiazolyl -N',N'-dimethylurea;

N-2 (4-methoxy-S-chlorothiazolyl) -N-acetyl-N-propenylurea;

N-Z(4-p-chlorophenylthiazolyl -N-methyl-N,N'-dimethylurea;

N-2 4-p-chlorophenylthiazolyl -N'-methylurea;

N-2 4-p-methoxyphenylthiazolyl -N'-tolylurea.

The compounds described have been found to have exceptional herbicidalproperties. For this purpose, they find widespread application forinhibiting the growth or even destroying of all kinds of plants, pests,such as weeds, brushwood and undesirable shrubbery.

The amount of the compound required to achieve the desired herbicidaleffect will depend upon a number of factors such as the nature of thecompound itself, the resistance of the species of plants, thecomposition of the ground, the state of growth of the plant at the timethat treatment is effected, that is, a complete kill or only a selectivekill.

The compounds may thus be employed as a total herbicide or as aselective herbicide or as a growth regulator. There is a wide range ofpossible applications depending upon the chemical nature and dosage ofthe herbicidal compound utilized. The compounds may be applied eitherprior to the seeding or planting of the cultures or application can bemade as a preemergence treatment after seeding but before the culturesor weeds break through the ground or as a post-emergence treatment afterthe plants break through the ground. In general, the compounds may beapplied at any stage of plant growth best adapted to the problem to besolved and the nature of the cultivated plants.

In practice, the substituted thiazolylureas or thiazolylthioureas of thepresent invention are utilized in amounts within the range of 0.1 to 30kilograms per hectare a d preferably within the range of 0.5 to 20kilograms per hectare. The optimum dosage will depend upon the intendedaim, the type of application, the nature of the plant pests intended tobe destroyed and their stage of growth and upon the persistence of thedesired herbicidal action.

An interesting property of certain of the thiazolylureas andthiazolylthioureas of this invention resides in the persistence of theirherbicidal action. Compounds of the type described, when suitablyformulated, remain effective to prevent weed growth from several weeksto several months. This effectiveness over a long period of time is avery desirable feature of the compounds of this invention since weedcontrol can be maintained throughout the growing season.

Another surprising property of the compounds of this invention is thehighly specific character of their action on vegetation. When applied inproper dosages, the compounds are effective to destroy certain weedswhich are dicotyledoneae without damaging other cultivated species ofdicotyledoneae. Weed plants belonging to the graminaceae family may bedestroyed in cereal cultures like wheat, barley, oats and Indian corn,without harming such cultures. The thiazolylureas and thioureas of thisinvention may be employed alone or in mixtures such as solutions inorganic solvents, or as dispersions or emulsions of the oil-in-water orwater-in-oil types or as suspensions in aqueous medium. They may beformulated into pastes or mixed with powders for dusting or they may beapplied as granules in mixtures containing talcum, kaolin, or othersuitable filler.

Such solutions, dispersions, pastes, powders or granules may beformulated to contain different proportions of the active componentdepending upon the intended use. As previously described, suchcompositions may be formulated to contain the active ingredient in anamount within the range of 0.5 to percent by weight of the composition.

The compounds of this invention may also be mixed with other additiveswhich are also active or toxic with respect to plants. Certain of theseadditives may be in the form of solids, as represented by sodiumchlorate or the borates or in the form of liquids such as tar oilderivatives (creosotes), substituted or unsubstituted phenols, crude oilderivatives such as kerosene, gas oil, fuel oil and the like. Thecompounds may be formulated with other useful additives such asfertilizers which contain the usual elements of phosphorus, potassiumand nitrogen (with or without trace elements such as Fe, Mn, Zn, Mg, Coand Cu.

In accordance with an important feature of this invention, thethiazolylureas or thioureas may be combined to give a synergisticreaction with other known pesticides in the form of fungicides,bactericides, insecticides and herbicidies to increase the biologicalactivity. It is possible to formulate the treating composition tocontain one or more of the pesticides described having differentchemical structures and biological activities and which may be selectedfrom the group consisting of nitrophenols, chlorophenols,chloronitrophenols, halogenated aryloxyalkylcarboxylic acids,phenylalkylcarboxylic acids, halogenated benzoic acids and derivativesthereof such as the corresponding salts, esters amines amides andimides, halogenated carbamates, substituted thiocarbamates andthiolocarbarnates, esters of dithiocarbamic acid, alkyl isothiocyanates,mono-or disubstituted amides; di-, tri-, or tetrasubstituted aralkylureas, substituted triazines, aminotriazole, substituted benzothiazole,hydrazides, uracil derivatives, pyridinium salts, quaternary ammoniumsalts, inorganic herbicides such as bichromates, alkali metal cyanates,Na AsO NH SO NH etc., as represented by the following specificcompounds: pentachlorophenol; dinitrocresol; dinitrobutyl phenol; Na 2,4dichlorophenoxyaoetate; Na2,3,G-trichlorobenzoate; Na monochloroortrichloroacetate; isopropyl N-phenylcarbamate; ethylN,N-dipropylthiolocarbamate; N,N-dimethyldiphenylacetamide;N-phenyl-N,N-dlimethylurea; 2-chloro-2,6-bis- (ethylamino)-s-tria-zine;3-amino-l,2,4triazole', 2,6-dichlorobenzonitrile, maleic hydrazide;2-chlorobenzothiazole; 1,1'-ethylene dibromide; 2,2'-bipyridinium;methyl isothiocyanate.

In accordance with another feature of the invention, modifications canbe made of the various formulations to include one or more surfaceactive agents of the anionic, cationic or nonionic types, as representedby: Na alkylnaphthalenesulfonate, Na cetyl sulfate, Na oleyl sulfate, Nalauryl sulfate, Na N-rnethyl-N-oleyltaurate, Na oleyl isothionate, Naligninsulfonate, Na dodecylbenzenesulfonate, alkanolamides of fattyacids, Na di(2-ethylhexyl)sulfosuccinate, sulfonated monoglycerides fromcoconut oils, alkyltrimethylammonium chlorides,alkylbenzyldimethylammonium chloride, cetyltrirnethylammonium bromide,the methoxysulfonate of oleyldiethylmethylethylenediamine; laurylpolyethylene glycol ether; ethers from polyoxyethylene andalkylphenols,'polyethylene glycol stearate, polypropylene glycolstearate, condensation products of polypropylene glycol and ethyleneoxide, esters of polyethylene glycol and of tall oil acids, sorbitolmonopalmitate, sorbitol monooleate, tris(polyoxyethylene)sorbitolmonolaurate, tris(polyoxyethylene)- sorbitol monooleate; thecondensation product of n-dodecyl mercaptan with ethylene oxide.

The following examples of the preparation and use of the compounds ofthis invention are given by way of illustration, but not by way oflimitation:

EXAMPLE 1 Preparation of N-2(S-chlorothiazolyl)-N'-methylurea To athoroughly agitated solution of 9.5 grams of 2- amino-S-chlorothiazolein 35 ml. dimethyl sulfoxide (DMSO), 4.8 grams methyl isocyanate isadded dropwise with an accompanying rise in temperature to about 56 C.When the addition is finished, the mixture is cooled to 45 C. andmaintained at this temperature for about 1 hour by the addition of heat,if necessary. The solvent is distilled off in vacuum and the reside istaken up in 500 ml. of boiling acetone in the presence of vegetablecharcoal. The warm solution is filtered and white shiny crystals areformed in the filtrate upon cooling.

The dried crystals have a melting point of 271-2715 C. The yield of thecompound is about 50 percent by weight calculated on the basis of thestarting amine. The following is an analysis in percent by Weight of thecompound produced in accordance with this example as compared to thetheoretical compound calculated for Compound of Example 1 (percent): C,31.83; H, 3.19; Cl, 18.39; S, 16.70. Calculated (percent): C, 31.33; H,3.15; CI, 18.50; S, 16.73.

EXAMPLE 2 Preparation of N-2 5-chloro-4-methylthiazolyl) N'-pheny1urea 5grams of 2-amino-5-chloro-4-methy1thiazole is dissolved in 50 ml. of CHCN. 4.1 grams of phenyl isocyanate is added dropwise at room temperaturewith an accompanying rise in temperature to 50 C. This temperature ismaintained for 2 hours, the mixture is cooled and the precipitate iscollected and dried. It is purified by recrystallization from CH CN anddecolorized in the presence of vegetable charcoal. 6.75 grams of N-2(5-chloro-4-methylthiazoly1)-Nphenylurea is obtained in the form of a whitepowder having a melting point of 252 C., providing a yield of about 75percent by weight. The compound is given the empirical formula of C HCIN OS Compound of Example 2 (percent): C, 49.34; H, 3.76; N, 15.70; Cl,13.25. Calculated (percent): C, 49.46; H, 3.62; N, 15.90; Cl, 13.29.

EXAMPLE 3 Preparation of N-2 5 -methylthiazo1yl -N'-phenylurea To asuspension of 7 grams of Z-arnino-S-methylthiazole in 50 ml. of CH CN7.7 grams of phenyl isocyanate is added slowly with an accompanyingtemperature rise to about 48 C. The amine becomes dissolved during thecourse of the addition and the solution is maintained at 48 C. for about20 minutes. In the course of the reaction, an insoluble product isproduced until finally the whole mixture stitfens. The mixture isallowed to remain for about 4 hours after which the crystals areseparated and dried and Washed with CH CN and again dried in vacuum.12.45 grams of N-2(S-rnethylthiazolyl)N-phenylurea is secured in theform of a white crystalline powder having a melting point of l-l96 C.corresponding to a yield of about 87 percent by weight.

EXAMPLE 4 Preparation of N-Z-thiazolyl-N'-phenylurea The procedurecorresponds to that of Example 3 except that Z-arninothiazole isemployed instead of the 2-amino- S-methylthiazole. The productN-2-thiazolyl-N'-phenylurea is obtained in the form of a fine Whitepowder having a melting point of about 171 C. which melting point israised to 173 C. after recrystallization from CH COOH of 50% strength.The yield of crude product corresponds to about 96%. The following isthe analysis of the compound as compared to the empirical formula C H NOS:

Compound of Example 4 (percent): C, 54.78; H, 4.14; N, 19.16; S, 14.62.Calculated (percent): C, 54.77; H, 3.91; N, 19.23; S, 14.48.

EXAMPLE 5 Preparation of N-Z-thiazolyl-N'-methylurea To a suspension of10 grams of Z-aminothiazole in 25 ml. of CH CN, containing two drops oftriethylamine, 6 grams of methyl isocyanate is slowly added by pouring.The reaction is slightly exothermic and the temperature rises to about66 C. At the end of the addition, the mixture is cooled to 50 C. andmaintained at this temperature for 1% hours. TheN-2-thiazolyl-N'-methylurea separates in the form of a White crystallineprecipitate which is air dried and then dried in vacuum. The yield ofcrude product, having a melting point of 215 C., is 15.45 grams or about78%. After recrystallization in absolute alcohol at 30 C., the meltingpoint is raised to 218 C. A final product in the form of shiny whiteneedles is obtained in an overall yield of 94%. The following is theanalysis of the compound N-2-thiazolyl-N'-methylurea produced inaccordance with this example as compared to the empirical formulaC5H7N3OS:

Compound of Example 5 (percent): C, 38.20; H, 4.49; N, 28.73; 0, 10.18;S, 20.40. Calculated (percent): C, 37.77; H, 4.35; N, 28.84; 0, 10.52;S, 20.90.

7 EXAMPLE 6 Preparation of N-2- S-thiocyanato thiazolyl-N'- methylurea580 ml. of CH CN is warmed to 80 C. and 33.6 grams of2-amino-5-thiocyanatothiazole is dissolved therein. 17.1 grams of methylisocyanate is added with constant stirring and the stirring is continuedwhile the mixture is maintained at 80 C. for 8 hours.

Upon cooling, the substituted urea precipitates in the form of a fine,slightly pinkish powder which is filtered and dried. The crudeN-2-(5-thiocyanato)thiazolyl-N'- methylurea has a melting point of 225C. and is secured in the amount of 38.9 grams or about 86.5% yield.Recrystallization in methanol yields a final product in the form ofsmall shiny flakes having a yellow coloration and a melting point of 226C.

The results of the elemental analysis of the compound as compared to theempirical formula C H NflS is set forth in the following table:

Compound of Example 6 (percent): C, 33.63; H, 2.82; N, 26.15; S, 29.92.Calculated (percent): C, 33.42; H, 2.74; N, 25.96; S, 29.90.

EXAMPLE 7 Preparation of N-2-(5-carbethoxy-4-methylthiazolyl)-N'-methylurea By proceeding in accordance with Example 1 but using as thereagents methyl isocyanate and 2-amino-4-methyl- S-carbethoxy-thiazole,the above compound is obtained having a melting point of 262 C. afterrecrystallization from absolute ethyl alcohol, corresponding to a yieldof about 75.5%. The analysis of the compound produced furnished thefollowing values compared to the empirical formula CQH13N303S:

Compound of Example 7 (percent): C, 44.43; H, 5.38; N, 17.27; 0, 19.72;S, 13.17. Calculated (percent): C, 44.03; H, 4.83; N, 17.44; 0, 19.92;S, 13.50.

EXAMPLE 8 Preparation of N-2(4-methylthiazolyl)-N'-methylurea Theprocedure of Example is followed but in which the reagents are methylisocyanate and 2-amino-4-methylthiazole. The above compound is obtainedin a yield of 93% having a melting point of 212 C. afterrecrystallization from CH,CN.

The results of the analysis of the compound produced by the example ascompared to the empirical formula C H N OS is as follows:

Compound of Example 8 (percent): C, 42.09; H, 5.30; N, 24.54; 0, 9.34;S, 18.73. Calculated (percent): C, 41,81; H, 5.08; N, 24.83; 0, 9.32; S,18.67.

EXAMPLE 9 Preparation of N-2(4-trifiuoromethylthiazolyl)N'- methylureaThe procedure is in accordance with Example 6 but in which the reagentsare methyl isocyanate and 2-amino-4- trifluoromethylthiazole. Theproduct identified above has a melting point of 254 C. afterrecrystallization from isopropanol and is obtained in a yield of about57%.

The analysis of the compound produced by this example as compared to theemipircal formula C H F N OS is set forth in the following table:

Compound of Example 9 (percent): C, 32.00; H, 2.69; N, 18.66; F, 25.31;S, 14.24. Calculated (percent): C, 32.23; H, 2.88; N, 18.76; F, 25.20;8, 14.45.

EXAMPLE 10 Preparation of N-2(4-p-chlorophenylthiazolyl)-N'- methylureaThe procedure is in accordance with Example 5 but the reagents employedare methyl isocyanate and 2-amino-4- (p-chlorophenylthiazole). A yieldof 97% is obtained of the compoundN-2(4-p-chlorophenylthiazolyl)-N'-methylurea, having a melting point of232.5 C. after recrystallization from acetonitrile.

The analysis of the compound produced as compared to the empiricalformula C H ClN OS is as follows:

Compound of Example 10 (percent): C, 49.34; H, 3.76; Cl, 13.24; N,15.69; S, 11.97. Calculated (percent): C, 49.16; H, 3.64; CI, 13.30; N,15.52; S, 11.96.

EXAMPLE 1 1 Preparation of N-Z(5-chloro-4-methylthiazolyl)-N-methylureaA mixture of 6.1 grams of 2-amino-5-chloro-4-methyl-thiazolechlorohydrate and 25 ml. pyridine is heated to 3540 C. 2.1 grams ofmethyl isocyanate is added over a period of 15 minutes. The mixture isheated with stirring for 3 hours to 50 C. and it is then cooled andrapidly poured over 500 grams of ice. The precipitate formed is filteredand recrystallized from CH CN. A yield of 75% is obtained of thecompound N-2(5-chloro-4- methylthiazolyl-N' methylurea in the form of awhite powder having melting point of 237 C.

The analysis of the compound as compared to the empirical formula C HClN OS is as follows:

Compound of Example 11 (percent): C, 35.04; H, 3.92; N, 20.43; Cl,17.24; S, 15.59. Calculated (percent): C, 35.06; H, 3.70; N, 20.23; Cl,17.09; S, 15.64.

EXAMPLE 12 Preparation of N-2(S-chlorothiazolyl)-N'-methylthiourea 1.5grams of methyl isothiocyanate and 2.7 grams of 2-amino-5-chlorothiazoleare dissolved in 42 grams pyridine. The solution is heated for 5 hoursunder reflux and then it is cooled and poured into an excess of water.

EXAMPLE 13 Preparation of N-2(5-chloro 4 methylthiazolyl) N,N'-dimethylurea 38.4 grams of pyridine is mixed with 22.7 gramsdimethylcarbamyl chloride and cooled to 5 C. 29.7 grams of2-amino-5-chloro-4-methylthiazole is added in small increments. Thereaction is slightly exothermic so that the temperature rises to about16 C. The materials are allowed to stand for 1 hour and then heated for3 hours at 60 C. The mixture is then allowed to cool and poured into 1liter of ice water with thorough stirring so as to prevent the formationof lumps. The product N-2(5- chloro-4 methylthiazolyl)-N',Ndirnethylurea is separated by filtration and recrystallized from 1.5liters of CHgCOOH of 50% strength. The crystals are washed with wateruntil made neutral and the resulting compound obtained in a yield of42.5% has a melting point of 163 C.

The analysis of the compound as compared to the empirical formula C HClN OS is as follows:

Compound of Example 13 (percent): C, 38.26; H, 4.59; Cl, 16.15; S,14.59. Calculated (percent): C, 38.29; H, 4.22; Cl, 16.15; S, 14.59.

9 EXAMPLE 14 Preparation of N-2(4,5-dimethylthiazolyl)-N'-methylurea Byusing the method of Example but employing as In Table 3, the activeproduct is applied in the form of a sludge containing 5% by weight of awettable powder of N-2(S-chlorothiazolyl)-N-methylurea.

TABLE 3 Rcsults after 10 days doses in kgJhectare of active materialResults after 30 days doses in kg./hectare oi active material EXAMPLES-20 Biological experiments and tests were conducted with variousgreenhouse plants using N-2(5-chlorothiazolyl- N'-rnethylurea in fourdifierent dosages, as set forth in the following tables. Two techniquesof treatment were employed, as follows:

(a) the pre-emergence treatment, i.e. after seeding but before theplants break through the ground (see Tables 1 to 3);

(b) the post-emergence treatment, i.e. after the plants have brokenthrough the soil, when each seed has developed into a young plant ofbetween 5 and 15 cm. in height (see Tables 4 to 6).

The active product was formulated into an aqueous suspension from awettable powder containing by weight of the active compound and appliedto the plants by atomization.

The results noted and the evaluations are set forth in the followingtables as percent of destruction of the treated vegetation.

TABLE i.PRE-EMERGENCE TREATMENT OF SEVERAL PLANTS WHICH BELONG TO THEGRAMINACEAE AND WERE CULTIVATED IN A GREENHOUSE, THE RESULTS ANDEVALUATIONS BEING MADE 37 DAYS AFTER TREATMENT Doses in kg./hectare ofactive material Species of treated plants 0. 5 l 2 4 Barley (Hordeumdistichum) 0 i5 100 Indian corn (Zen maps) 0 [2b] 15 20 80 Oats (Arenasatiua)- 0 20 100 100 Wheat (Triticum vulgar 0 100 100 Wild oats(Avenajatuu) 5 30 100 100 Wild millet (Echinochloa crusqalli). 5 65 98I8 Millet (Panicum miliaceu'm). 6 98 100 100 Ryerass (Lolium italicwm)-l 75 98 100 100 Stan er Foxtail (Alopecurua agrestis) 90 100 100 ill)TABLE 2.-PRE-EMERGENCE TREATMENT OF VARIOUS PLANTS WHICH AREDICOTYLEDONEAE AND WERE CULTIVATED IN A GREENHOUSE, THE EVALUATIONSBEING MADE 37 DAYS AFTER TREATMENT Doses of the active material inkgJhectare Species of plant treated 0.5 1 2 4 Peas (Pismn salivmn) 0 0 D3 Tomatoes (Solarium eeculentmn) 0 0 95 Carrots (Daucus carotta) 100 100100 Linseed (linum usitalissimum) 100 100 100 Buckwheat (Polygonumfaqopyru'm 98 100 100 Amaranth (A'mcranthus species) 100 100 ml) Rape(Branaz'cu napus) ml) 100 100 For the great nasturtium, as recognizablefrom this table, no destruction occurred, but a slight phytotoxicity wasnoted starting with the dosage of 10 kg./hectare of the active material.

Tables 1 to 3 show that N-2(5-chlorothiazolyl)-N'- methylurea hasexceptional herbicide efiect which can destroy species belonging both tothe graminaceae as well as to the dicotyledoneae. Thus it is applicableagainst a widespectrum of plants. Furthermore, this herbicide enjoysexceptional efficiency because it is able to destroy up to 100% of suchspecies as slender foxtail, rape and buckwheat when employed in dosagesas low as 0.5 kg./hectare in the pre-emergence treatment. This compoundalso exhibits a selective herbicidal action due to an unexpected andremarkable fact. For example, when applied in the dosage of 0.5kg./hectare, 90% of the foxtail is destroyed whereas the wheat remainsundamaged. This herbicide shows a good selectivity with respect to peasand tomatoes in pre-emergence treatment, whereas, at the same dosage,other dicotyledoneae such as carrots, linseed and rape are completelydestroyed. At dosages of 4 kg./hectare, all of the test plants with theexception of the peas and the great nasturtium, are prac ticallydestroyed. Of considerable interest is the fact that the compound canfunction as a total weed removal agent.

The following Tables 4 and 5 present the results of post-emergencetreatments of various plants which are, respectively, graminaceae inTable 4 and dicotyledoneae in Table 5. The experiments were undertakenon greenhouse cultures with a wettable powder containing 20% of theactive ingredient N-2(5-chlorothiazolyl)-N'-methylurea. The evaluationsset forth in the tablet were made 34 days after treatment.

TABLE 4 Doses per hectare, in kg.ot active material Species of planttreated 0. 5 2 4 Wheat 0 0 0 0 ar1ey 0 0 0 0 Wild oats. O 0 0 it) Oats(1 0 0 20 Indian corn- 0 0 0 25 Rye grass 5 96 Slender install 10 92 D898 Wild millet 80 100 100 100 TAB LE 5 Doses per hectare, in kg. ofactive material Species of plant treated 0 5 1 2 4 0 0 0 0 0 0 l) 5 5 2035 70 5 40 B0 98 Buckwheat. 15 60 65 U0 TABLE 6.POST-EMERGENCE TREATMENTOF VARIOUS PLANTS WITH AQUEOUS DISPERSIONS CONTAINING BY WEIGHT OF THEACTIVE MATERIAL TABLE 7.PRE-EMERGENCY TREATMENT OF VARIOUS PLANTS WHICHARE GRAMINAOEAE, SETTING FORTH OBSERVATIONS 41 DAYS AFTER TREATMENTDoses per Species of plant treated It will be recognized from the abovetable that for the great nasturtium no destruction occurs at any of thedosages although a slight phytotoxicity appears with the dosage ofkgJhectare of active material.

The results set forth in Tables 4 to 6 indicate that postemergencetreatment with the herbicide destroys 92% of the slender foxtail whenapplied in a dosage of 1 kg./ hectare and that it is still fullyselective in that it does not destroy wheat, barley and wild oats evenat twice the dosage. At a dosage of 2.5 kg./hectare, wild mustard iscompletely destroyed within one month after treatment whereas oatsremains unafl'ected.

EXAMPLES 21-23 Field experiments were conducted withN-2(5-chlorothiazolyl)-N-methylurea as the active material applied tothe plants in the same manner as described in Examples -20.

(a) Barley in spring.As the stage of development of three leaves, barleyis treated by applying 0.75 to 1.25 kg./hectare of active material. Theaccompanying weeds were represented by goosefoot (Chemopodium species)and by wild radish (Raphanus raphanistrum). The effectiveness of weedremoval was very good 64 days after treatment.

(b) Wheat in autumn.-The pre-emergence treatment in dosages of 1.5kg./hectare was employed and it was noted that after three months theweed-killing effect was selective with respect to wheat. Slender foxtailand wild radish were destroyed substantially completely.

(c) With peas.-Treatmer1t was made as soon as the plants broke throughthe ground by application of the active material in dosages of 1 to 2kgJhectare. The selectivity was perfect in that 45 days after treatmentthe herbicidal efiiciency was exhibited by the fact that knotweed(Polygonum aviculare), black bindweed (Polygonum convulvulus) andgoosefoot (Chenopodium species) was completely destroyed without harm tothe pea plants.

EXAMPLES 24-27 The biological activity ofN-2(5-chloro-4-methylthiazolyl)-N'-methylurea upon various plants in thegreenhouse was tested with four different dosages, as indicated in thefollowing tables. Two different treatments were employed, namely, apro-emergence treatment after the seeding but before the plants brokethrough the ground, a post-emergence treatment after the plants hadbroken through the ground and when each plant was present as a youngplant (seedling) which was approximately between 5 to 15 cm. inheight.

The active material was applied by spraying from an aqueous suspensioncontaining by weight of the active material as a wettable powder. Theresults observed as expressed in the following table in percent ofdestruction of the treated plants.

Brl

Doses in kgJhectare oi active materials Species of treated plants 1 2 48 Wheat 0 0 0 0 Indian corn. 0 O 0 0 Wild mlllet. 0 0 0 15 Barley 0 0 070 Oats... 0 0 I0 25 Millet 0 0 10 98 Rye grass 0 20 90 100 SlenderioxtaiL 0 5 56 95 TABLE 8.PRE-EMERGENCY TREATMENT OF VARIOUSDICOTYLEDONEAE, OBSERVATIONS BEING MADE 41 DAYS AFTER TREATMENT Doses inkgJhectare of active materials Species of treated plants 1 2 4 B Peas 00 0 0 Green bean (Phaseolua mlgarisyflun 0 0 0 0 Tomatoes 0 0 0 25Common sunflower (Helianthus annuus) 0 5 0 35 Buckwheat e 0 0 5 40 R 0 010 98 The following Tables 9 and 10 set forth the results frompost-emergence treatments of various graminaceae in Table 9 anddicotyledoneae in Table 10, in the greenhouse. The results are thoseobserved 42 days after treatment.

TABLE 9 Doses in kgJhectare of active materials Species of treatedplants 1 2 4 8 Indian corn 0 0 0 0 0 0 0 50 0 0 20 34) 0 0 30 100 0 0 709D 0 20 50 100 t 0 24 50 98 Italian wild rye grass. 0 7D 95 100 TABLE 10Doses ln kg.lhectare of active materials Species of treated plants 1 2 48 Peas 0 0 0 D 0 0 0 0 0 0 0 50 0 30 40 40 0 30 70 90 60 60 60 60 60 6080 90 It will be seen from Tables 7 to 10 that a clearcut activity isachieved both for the pre-emergence as well as for the post-emergencetreatments when application is made in dosages between 4 to 8kg./hectare of the active material. In the pre-emergence treatment, aselective weed killing is observed in that wheat, Indian corn, greenbeans and peas remain undamaged (Tables 7 and 8) whereas the slenderfoxtail is destroyed in the amounts of $5- 95% and the Italian wild ryegrass in the amounts of 90100%. In the post-emergence treatment, aselective weed killing is obtained without harm to Indian corn and peas(Tables 9 and 10) while foxtail is destroyed in amounts up to 70-90% andwild rye grass in amounts up to 9Sl00%.

EXAMPLES 28-33 According to the method used in Examples 15-20, the whichform the subject matter of this invention were tested with respect toplants using a dosage of 8 kg./hectare of active material. Tables 11 and12 set forth the results obtained, expressed in percent destruction ofthe treated plants.

TABLE 11.PRE-EMERGENCE TREATMENT OF VARIOUS GRAMINACEAE IN WHICH THERESULTS SET FORTH WERE OBSERVED 46 DAYS AFTER EDONEAE, IN WHICH THERESULTS WERE OBSERVATIONS MADE 46 DAYS AFTER TREATMENT Example Activematerial tested N-Bbkmeth l- N-2(5-el11oro-4-N-2t4-trinuorothlazotlgllmsthylthlazol l)- methylthiazolynme ylureaN,N'-dimet yl- N-methylurea urea Examples 29 and 32 show that treatmentis selective in that it does not destroy wheat, Indian corn, oats andbarley, green beans, peas and sunflower, whereas destruction is observedof slender foxtail up to 95%, Italian wild rye grass up to 70% and wildmillet up to 80%.

The compounds of Examples 30 and 33 show herbicidal activity but withouttoo much selectivity. All of the millet and rape are destroyed and onlyIndian corn remains fully resistant.

The compounds of Examples 28 and 31 are selective in that wheat, Indiancorn, millet, barley and green beans are not destroyed while herbicidalelfect in the order of 85% is secured with respect to rape.

jEXAMPLE 34 Treatment is elfected in accordance with Examples 15- 20 butat a dosage of 10 kgJhectare, using as the active ingredient N 2thiazolyl N methylurea. The active ingredient completely destroyedmillet in a pre-emergence treatment.

It will be seen from the foregoing that a new series of compounds areprovided which have shown marked activity as a herbicide in managingplant growth and in the destruction of undesirable weeds and plantsconnected with plant growth. The compounds of this invention exhibit animportant degree of selectivity with respect to their herbicidalactivity with various plants and combinations of plants.

It will be understood that changes may be made in the details offormulation and application without departing from the spirit of theinvention, especially as defined in the following claims.

We claim:

1. A thiazole derivative having the formula of hydrogen, halogen, alkyl,alkoxy or halogenated alkyl in which the alkyl and alkoxy groups containfrom 1-4 carbon atoms and in which at least one of the groups X and Y ishalogen, R is selected from the group consisting of hydrogen, alkylcontaining from 1-4 carbon atoms and alkenyl containing from 14 carbonatoms, R: and -R are selected from the group consisting of hydrogen,alkyl, alkenyl and alkynyl in which the alkyl, alkenyl and alkynylcontain from 14 carbon atoms, and Z is selected from the groupconsisting of oxygen and sulphur.

2. A thiazole derivative as claimed in claim 1 in which the compound isN-2-(5-ehlorothiazolyl)-N'-methylurea.

3. A thiazole derivative as claimed in claim 1 in which the compound isN 2 (5 chloro 4 methylthiazolyl)- N'-methylurea.

4. A thiazole derivative as claimed in claim 1 in which the compound isN 2(5 chlorothiazolyl) N methylthionrea.

5. A thiazole derivative as claimed in claim 1 in which the compound isN 2(5 chloro 4 methylthiazoyly)- N',N-dimethylurea.

References Cited The following references, cited by the Examiner, are ofrecord in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,755,285 7/1956 ONeill et a1. 260-306.8

FOREIGN PATENTS 14,593 10/1963 Japan 260306.8

OTHER REFERENCES DeGering, An Outline of Organic Nitrogen Compounds(Michigan, 1950), p. 438.

Bhargava et al., Bull. Chem. Soc. Japan, vol. 38, pp. 905-9 (1965).

Tefas et al., Chem. Abstracts, vol. 54, cols. 17376-7 (1960).

ALEX MAZEL, Primary Examiner R. J. GALLAGHER, Assistant Examiner UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N Reissue 27 DatedOctober 10.

Inventor(s) Jean-Claude Guillot et al.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Foreign Application Priority Data April 6, 1965 France. 12,116

Signed and sealed this 6th day of March 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents )RM PO-1050 (IO-69) USCOMM-DC 60376-fl69 u s oovsmmem PmmmoOFFICE 1969 muss-334

